The present application claims priority to German Application No. DE 102 04 471.6, filed on Feb. 5, 2002, which is hereby incorporated by reference in its entirety.
1. Field of the Invention
The present invention relates to an aqueous dispersion containing a silicon dioxide powder coated with cerium oxide. In addition, the present invention provides a method of producing an aqueous dispersion containing a silicon dioxide powder coated with cerium oxide and methods of using this aqueous dispersion for chemical-mechanical polishing.
2. Discussion of the Background
Cerium oxide dispersions obtained by calcining a cerium compound and subsequently grinding the oxides have been used for a long time for glass polishing. These dispersions typically have particle sizes of more than 1000 nm and large impurity contents. These dispersions are suitable for a coarse polishing of surfaces, but not for polishing of sensitive optical surfaces, semiconductor substrates, or integrated circuits (i.e., chemical-mechanical polishing, CMP).
Smaller cerium oxide particles may be obtained from a process, which has been denoted hydrothermal synthesis. In this process a cerium (III) salt is oxidatively converted, under the influence of temperature and pressure, to cerium oxide, which crystallizes out in the form of fine particles. The particle sizes of the cerium oxide obtained by this process are 80-100 nm (EP-A-947 469), 7-50 nm (U.S. Pat. No. 5,389,352), or less than 30 nm and greater than 60 nm (U.S. Pat. No. 5,772,780). A disadvantage of this method is that it requires the use of very dilute cerium (III) solutions as the starting material.
U.S. Pat. No. 5,891,205 discloses mixtures of silicon dioxide and cerium oxide, which has been produced by hydrothermal synthesis. In the process disclosed in this reference, the cerium oxide must first by deagglomerated using a mill and subsequently the resultant cerium oxide dispersion is mixed with a silicon dioxide dispersions based on silica sol. The mixture can then be used for planarising silicon discs. The disadvantages associated with this process include the high complexity and costs for the production of the fine-particle dispersion. In addition, the deagglomeration of the cerium oxide by using a mill carries a risk of impurity transfer into the dispersion. Furthermore, it is readily appreciated in the art that silicon dioxide dispersion based on silica sol have a higher proportion of impurities than those based on silicon dioxide produced pyrogenically.
U.S. Pat. No. 5,382,272 discloses the activation of silicon dioxide particles by adsorption of a few percent by weight, preferably 2% by weight, of a cerium or zirconium oxide dispersion. The special feature of this process is that the activating effect is accomplished by grinding a silicon dioxide dispersion with a commercially available cerium or zirconium oxide dispersion. The resultant mixed dispersion behaves like pure cerium oxide dispersions in polishing of semi-conductor substrates with a high removal rate, but without leaving any scratches on the surface to be polished. This method has an advantage over other common methods in that the costs associated therewith are reduced and implementation is relatively simple. However, this method also harbors distinct disadvantages, which are described in detail in WO 00/17 282 A1, such as the production of a dispersion with a narrow particle size range and difficulties in achieving reproducible polishing results.
U.S. Pat. No. 5,697,992 discloses the production of a powder containing abrasive particles and aqueous dispersions produced therefrom. The abrasive particles consist of silicon dioxide or aluminum oxide and a coating of cerium oxide. In this reference, the abrasive particles have an average particle size of 2 xcexcm or less. However, based on this disclosure, it is unclear whether the stated particle size refers to the powder or the dispersion. For silicon dioxide particles coated with cerium oxide a particle size of 0.6 xcexcm is given in one example. The metal oxides come from either a sol-gel or a pyrogenic process. A disadvantage of the process employed in this reference is caking of the metal oxide particles, particularly those of pyrogenic origin, when being coated with a cerium compound. As such, this leads to the formation of hard aggregates that are difficult to disperse. In the dispersion, this can lead to a very broad particle size distribution and occasionally to the detachment of parts of the coating in the form of cerium oxide during dispersion. Accordingly, the dispersion obtained by the disclosure of U.S. Pat. No. 5,697,992 are non-uniform and, with the continuing miniaturization in the semi-conductor industry, accordingly are of only limited suitability for reproducible polishing of oxide surfaces.
Accordingly, there remains a critical need in the area of chemical-mechanical polishing (CMP) for extraordinarily high activity of cerium oxide compared to silicon dioxide and other dielectric oxides.
Accordingly, it is an object of the present invention to provide an aqueous dispersion containing cerium oxide, which is simple to produce, has only a small proportion of impurities and has a reproducibly adjustable particle size.
This object may be achieved by an aqueous dispersion containing a powder obtained from a core of doped, pyrogenically produced silicon dioxide with a low structure, by mixing, preferably spraying, with a cerium salt solution or suspension, forming a cerium oxide coating, wherein the powder does not exceed an average secondary particle size of 0.2 xcexcm in the dispersion.
The above objects highlight certain aspects of the invention. Additional objects, aspects and embodiments of the invention are found in the following detailed description of the invention.
Unless specifically defined, all technical and scientific terms used herein have the same meaning as commonly understood by a skilled artisan in the field of semi-conductors.
All methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, with suitable methods and materials being described herein. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. Further, the materials, methods, and examples are illustrative only and are not intended to be limiting, unless otherwise specified.
The present invention is based in part on the Inventor""s surprising discovery that an extraordinarily high activity cerium oxide possessing high removal rates and good selectivities, which are useful in chemical mechanical polishing can be achieved by employing an aqueous dispersion comprising a powder having an average secondary particle size of 0.2 xcexcm obtained by a process comprising mixing a core consisting of doped, pyrogenically produced silicon dioxide having a low structure with a cerium salt solution or suspension to form a cerium oxide shell.
xe2x80x9cAqueous dispersionxe2x80x9d as used herein means a dispersion in which the main component of the liquid phase is water.
xe2x80x9cA core consisting of a doped, pyrogenically produced silicon dioxidexe2x80x9d as used herein means a core in which the doping is introduced by means of an aerosol of a salt solution or suspension containing the doping component. For an example of the production of such cores the artisan is referred to DE-A-196 50 500.
xe2x80x9cLow structurexe2x80x9d as used herein means that the core consists of many individual spherical primary particles that are fused together only to a small extent. A measure of the low structure is the DBP absorption (dibutyl phthalate absorption). This is less than 100 g DBP/100 g powder, the term powder here referring to the doped core. It is also possible for the end point to be undetectable in the DBP absorption. In a pyrogenically produced, undoped silicon dioxide with the same BET surface area, in which the primary particles are more markedly fused together, the DBP absorption is generally more than 150 g DBP/100 g powder. For example, the commercially available, pyrogenically produced silicon dioxide OX 50, from Degussa AG, has a DBP absorption of 160 g DBP/100 g powder.
For the DBP absorption the force uptake or torque (in Nm) of the rotating blades of the DBP measuring instrument is measured upon addition of defined quantities of DBP, comparable to a titration. This method gives a sharply defined maximum for pyrogenic metal oxides (e.g. titanium dioxide or silicon dioxide) with a subsequent drop at a specific addition of DBP. For particles with a very low degree of fusing, it is also possible for the measuring instrument to be unable to detect an end point.
It is also possible to detect the low structure of the core by transmission electron micrographs.
Within the context of the present invention, cerium chloride, cerium nitrate, cerium acetate, cerium carbonate, cerium oxalate, cerium sulfate, ammonium cerium sulfate, or ammonium cerium nitrate may be used as the cerium salt solution or suspension.
As part of the present invention the coating may be applied by mixing, or preferably spraying, the aqueous and/or alcoholic slurry of the core with a cerium salt solution or suspension. The reaction mixture is subsequently dried and optionally calcined. Under the reaction conditions the cerium salt solution or suspension is converted to cerium oxide. The cerium oxide coating may be fully or partly formed.
The content of doping component in the core is between 10 ppm and 10 wt. %. The content of cerium oxide in the coated core is between 10 ppm and 65 wt. %.
The BET surface area of the powder is between 5 and 600 m2/g.
The average secondary particle size in the dispersion according to the invention is less than 0.2 xcexcm. The average secondary particle size may be determined by dynamic light scattering, or other well-recognized techniques.
Cores, the doping component of which is an alkali oxide or an aluminium oxide, can preferably be used.
The solids content of the dispersion according to the invention depends primarily on the intended use. For example, to save transport costs, a dispersion with the highest possible solids content is desirable. In contrast, for certain applications, such as for polishing, dispersions with low solids contents are used. Accordingly, a solids content of 0.1 to 70 wt. % is preferred within the present invention, and the range between 1 and 30 wt. % is particularly preferred.
Within the purview of the present invention, the dispersion may also contain additives selected from the group consisting of pH-regulating substances (such as acids, bases and/or buffer systems), oxidizing agents, oxidation activators, corrosion inhibitors, abrasives, and/or surface-active substance.
The pH of the dispersion according to the present invention may be between 3 and 11.
A pH increase may be affected by the addition of alkali hydroxides or amines. Ammonium hydroxide, potassium hydroxide and tetramethylammonium hydroxide are particularly preferred.
By adding acids, the pH can be shifted into the acid range, i.e. to a pH of 3. Carboxylic acids of the general formula CnH2n+1CO2H, with n=0-6 or n=8, 10, 12, 14, 16, or dicarboxylic acids of the general formula HO2C(CH2)nCO2H, with n=0-4, or hydroxycarboxylic acids of the general formula R1R2C(OH)CO2H, with R1=H, R2=CH3, CH2CO2H, CH(OH)CO2H or glycolic acid, pyruvic acid, salicylic acid or mixtures of the above acids are preferably used for this purpose. Acetic acid, citric acid and salicylic acid are particularly preferred for this purpose.
The present invention also provides a process for the production of the dispersion described herein, where the powder is first pre-dispersed in an aqueous medium, optionally with the addition of additives, and the pre-dispersion is then dispersed, wherein the average secondary particle size in the dispersion is less than 0.2 xcexcm.
xe2x80x9cPre-dispersionxe2x80x9d as used herein means a dispersion with an average particle size of no more than 1 mm. High-speed mixers or toothed discs, for example, are suitable for pre-dispersing.
Rotor-stator machines, such as Ultra Turrax (IKA) or those from Ystral, are suitable for dispersing, as are ball mills and attrition mills.
Higher energy inputs are possible with a planetary kneader/mixer. However, the effectiveness of this system is linked to a sufficiently high viscosity of the mixture being worked to introduce the high shear energies required to break down the particles.
A high-pressure homogenizer can preferably be used to produce the dispersion according to the invention.
With high-pressure homogenizers, particularly fine-particle dispersions can be produced. In these devices, two pre-dispersed suspension streams under high pressure are depressurised using a nozzle. The two dispersion jets collide with each other exactly and the particles grind one another.
In another embodiment, the pre-dispersion is also placed under high pressure, but the particles collide with armored wall areas. The operation can be repeated as often as desired to obtain smaller particle sizes.
The invention also provides the use of the dispersion according to the present invention for the chemical-mechanical polishing of semi-conductor substrates or of layers applied thereon. In particular, the present invention provides a use of the dispersion for polishing of oxide and metallic layers, and in the shallow trench isolation process (STI process). In this process, after applying a silicon nitride layer, isolation structures are etched into the silicon layer of a wafer, the resulting grooves are then filled with silicon dioxide and excess silicon dioxide is removed by chemical-mechanical polishing.
It has thus been found that the powder obtained from doped, pyrogenically produced silicon dioxide particles with a low structure and a cerium salt solution or suspension can be reproducibly dispersed to secondary particle sizes of no more than 0.2 xcexcm in an aqueous medium without any cerium oxide being detached and without any coarse particles forming. Such a result is surprising, as for example a dispersion obtained in accordance with U.S. Pat. No. 5,697,992 containing undoped silicon dioxide as the core cannot be reproducibly dispersed and cerium oxide becomes detached.
Having generally described this invention, a further understanding can be obtained by reference to certain specific examples, which are provided herein for purposes of illustration only, and are not intended to be limiting unless otherwise specified.